Sulfuric Acid → Methyl 4-hydroxy-3-methylbenzoate

HRID 220819

반응식

HRID 220819 반응식
[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7](N)=[C:6]([CH3:11])[CH:5]=1.S(=O)(=O)(O)[OH:14].N([O-])=O.[Na+].NC(N)=O>O.[N+]([O-])([O-])=O.[Cu+2].[N+]([O-])([O-])=O.[Cu]=O>[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7]([OH:14])=[C:6]([CH3:11])[CH:5]=1

참가 물질

8

반응물 4

HCID 1118Sulfuric AcidHCID 1176UreaHCID 2736799Methyl 4-amino-3-methylbenzoateHCID 23668193Sodium Nitrite

생성물 1

HCID 11240684Methyl 4-hydroxy-3-methylbenzoate수율 42%

시약·촉매·용매 3

HCID 14829Copper oxide촉매HCID 18616Cupric nitrate촉매HCID 962Water용매2회

반응 조건

온도
0 °C

실험 절차

4-Amino-3-methyl-benzoic acid methyl ester (5.25 g, 32.0 mmol) was treated with a 35% solution of sulphuric acid (50 ml) and the mixture was stirred and heated until dissolution then cooled to 0° C. Sodium nitrite (2.82 g, 41.6 mmol) in water (50 ml) was added dropwise and the mixture was stirred for 5 min at 0° C. Urea was added to destroy the excess nitrite. Copper nitrate (121 g, 320 mmol) in water (11) was added then copper oxide (4.25 g, 32.0 mmol). The mixture was warmed up to room temperature over 30 min and extracted with EtOAc (×3). The organics were combined, washed with brine, dried and concentrated in vacuo. The residue was purified by flash chromatography on silica gel (eluant; 30% EtOAc:70% hexane) to yield the title compound (2.2 g, 42%).

후처리

  1. temperatureheated until dissolution
  2. stirringthe mixture was stirred for 5 min at 0° C
  3. customto destroy the excess nitrite
  4. temperatureThe mixture was warmed up to room temperature over 30 min
  5. extractionextracted with EtOAc (×3)
  6. washwashed with brine
  7. customdried
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified by flash chromatography on silica gel (eluant; 30% EtOAc:70% hexane)

출처 및 근거

ORD 기록
ord-c0232a661d8649d69561cda858228fa9
출처 데이터셋
uspto-grants-2012_06
특허 번호
US08202858B2

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